Catalyst and process for dehydrogenation of hydrocarbons



Patented May 13, 1947 CATALYST AND PROCESS FOR DEHYDRO- GENATION OF HYDROCARBONS Peter William Reynolds, Arthur William Charles Taylor, and John George Mackay Bremner, Norton-on-Tees, England, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application December 21, 1942, Se-

rial No. 469,718. In Great Britain August 25,

This invention relates to catalysts suitable for use in dehydrogenation reactions and especially 4 Claims. (61. 260-6833) in the dehydrogenation of hydrocarbons to olefines and. diolefines containing the same number of carbon atoms.

Catalysts essentially consisting of or containing substantial amounts of oxides of aluminum and chromium are known to be suitable for the dehydrogenation of hydrocarbons. The methods disclosed for the preparation of these catalysts include, for example, that of impregnating 'Activated Alumina, e. g., in the form of porous calcined granules, with a chromic acid solution.

These known catalysts when used for example in the dehydrogenation oi paraflln hydrocarbons to the corresponding oleflnes, deteriorate in activity and have carbonaceous material deposited on them during the dehydrogenation, but theycan be regenerated by interrupting the dehydrogenation process and passing an oxygen-containing gas over them at an elevated temperature.

In practice, therefore, thev dehydrogenation is carried out in a series oi cycles of alternating periods of dehydrogenation and regeneration. The decrease in activity which occurs from the moment when dehydrogenation is commenced to the moment when it is interrupted and regeneration started, is hereinafter termed "intracyclic deterioration.

We have found that when these known catalysts are used for many cycles of dehydrogenation and regeneration, a decrease in the mean activity in each dehydrogenation period gradually becomes evident. The regeneration process, therefore, does not fully restore the activity oi these known catalysts. The degree of restoration obtained by the regeneration process decreases with increase in temperature or the dehydrogenation and-the regeneration.

In co-pending application Serial Number 398,680, filed June 18, 1941, now U. 8. Patent 2,382,394 issued August 14, 1945, there is described an improved catalyst suitable for dehydrogenation reactions which comprises as its essential constituent a product obtained by cautlous thermal decomposition of a precipitate produced from an aqueous solution containing an aluminum salt, together with ammonium chromate, ammonium dichromate or chromium trioxide, by adding thereto ammonia, ammonium bicarbonate or ammonium carbonate in an amount at least sumcient to give substantially complete precipitation of the aluminium.

We have now found a catalyst comparable with that described in copending application Serial Number 398,680, which for any given temperature of dehydrogenation and regeneration can be more completely regenerated than the known catalysts can be under the same conditions, and which moreover, when employed at temperatures of the order of 500 C. to 600 C. does not show any appreciable fall in mean activity .per cycle, after use in numerous alternate cycles of dehydrogenation and regeneration.

The catalyst of the present invention comprises as its essential constituent a product obtained by the cautious thermal decomposition of a precipitate produced from an aqueous solution containing an aluminium salt by adding thereto ammonia, ammonium bicarbonate or ammonium carbonate in an amount at least sufilcient to give substantially complete precipitation of the aluminium, the said aqueous solution being substantially free from any chromate, dichromate or chromiumtrioxide during the precipitation step, the said precipitate being impregnated with ammonium chromate or ammonium dichromate before the cautious thermal decomposition step.

Aluminium nitrate has been found to be a convenient aluminium salt for use in the preparation of the catalyst. Any soluble aluminium salt may, however, be used, e. g., aluminium chloride or its dehydrated forms, or aluminium sulphate.

The substantially complete precipitation of the aluminium with ammonia or its carbonate salts may be carried out at any temperature from the freezing point to the boiling point of the solution. Ammonia may be used either as a gas or in aqueous solution, while ammonium bicarbonate and ammonium carbonate are most conveniently used as solutions in water. The amount of precipitating agent does not appear to be critical, but it is preferred to add just sumcient to obtain substantially complete precipitation. The precipitate, after separation from the mother liquor, should not be subjected to any extensive washing and in general it is desirable that the precipitate should not be washed at all.

The precipitate, after separation of the mother liquor, may be impregnated with ammonium chromate or ammonium dichromate in any convenient manner, for example by suspending it in an aqueous solution of the desired salt, impregnation being assisted by stirring the suspension.

The thermal decomposition of the precipitate is carried out by heating it slightly in order to start the reaction," and then continuing to heat carefully until the reaction is substantially complete. In view of the exothermal nature of the development of high local temperatures, for example. by suitable disposition or agitation of the precipitate. It appears that the decomposition should take iplaw at as low a temperature as possible for the best results. The decomposition is conveniently carried out in air, but other atmospheres, such as steam, nitrogen or hydrogen, may be used.

We have further found that intracyclio deterioration of the catalyst and carbonaceous deposition can be decreased by the presence in the catalyst of a compound of the alkali metals or the chromite, chromate, or dichromate of zinc.

The chromates of the alkali metals have been found to be better than other alkali metal compounds, and the compounds of zinc hereinbefore mentioned. Potassium compounds in general appear to give better results than the corresponding compounds of the other alkali metals and potassium chromate is outstandingly better than all other compounds tested,

In the early stages of the life of a catalyst containing potassium chromate, carbon deposition is very small and lntracyclic deterioration is almost absent. On prolonged subjection to alternate cycles of dehydrogenation and regeneration, carbon deposition increases to a limiting value, and intracyclic deterioration appears, but both are lower than for a catalyst containing no potassium chromate.

In general the alkali metal compounds should be present in an amount by weight between 0.05% and 5.0% of the product obtained by the thermal decomposition hereinbefore described. The corresponding percentages in the case of the zinc compounds in general lie between 0.05% and 10.0%.

The alkali metal and zinc compounds may be introduced into the catalyst in any suitable manner, e, g., by addition as such or by production in situ, and at any convenient stage in or after the manufacture of the essential constituent of the catalyst. We prefer, however, to mix the alkali metal and zinc compounds with the previously prepared essential constituent, make the mixture into a slurry with water, and finally dry it.

The catalysts of this invention may have incorporated in them other compounds such as the oxides of magnesium, aluminum, and zinc, and may be used supported on suitable carriers or in the form of granules or as pellets.

The activity of the catalysts of this invention is influenced by the amount of water vapour present in the material to be hydrogenated. For any given raw material, the amounts of water which are suitable can easily be determined by a few simple experiments.

As examples of dehydrogenation processes for which our catalysts are useful, there may be cited the dehydrogenation oi hydrocarbons such as the conversion of paraflln hydrocarbons to olefines containing the same number oi carbon Example 1490 grams of aluminium nitrate (A1(NO3)3.9H2O) were dissolved, in 2,000 grams of water, and

.61. aqueous ammonia. containing 25% by weight of NH; was added to it until precipitation was complete, The precipitate was filtered, washed with 1 litre of water and then placed in a solution of 756 grams of ammonium dichromate in 3,000 grams of water and the whole thoroughly stirred for 1 hour. from the solution by filtration, and without being washed. -The dried precipitate was then cautiously decomposed by heating it in small portions in a porcelain dish over a low flame; the powder being vigorously stirred to prevent excessive heating by bursts of spontaneous de-- composition. The highly exothermic decomposition began at 120 0., and was substantially completed by raising the temperature of the powder to 350 C. The material was finally heated in dry air to 500 0., maintained at this temperature for 1 hour, and cooled.

The powdered catalyst prepared in the manner described, was mixed with =t% by weight of aluminium stearate and pelleted to x cylinders. These were finall calcined in air up to 500 C., to remove the organic material of the pellcting lubricant.

Substantially pure propane, dried by passage over fused calcium chloride, was passed over this catalyst at the rate of 2000 volumes of propane (measured at 20 C., and 1 atmosphere pressure) per volume of catalyst space per hour, the temperature being maintained at 600 C. An average sample of the exit gas taken over the first halfhour of the run contained 21% olefines, oi which more than was propylene.

We claim:

1. The process for forming a dehydrogenation catalyst composition comprising the steps of adding to an aqueous aluminum salt solution, free of chromium, a substance selected from the group consisting of ammonia and carbonates of ammonia in an amount sufficient to precipitate substantially all of the aluminum present in said solution, impregnating the hydrous aluminum oxide precipitate with a substance selected from the group consisting of ammonium chromate and ammonium dichromate, adding to the resulting impregnated hydrous aluminum oxide 3. minor amount of a substance selected from the group consisting of a, chromite, chromate and dichromate of zinc and alkali metals, and then cautiously thermally decomposing the resulting product.

2. The process for forming a dehydrogenation catalyst composition which comprises adding to an aqueous aluminum salt solution, free of chromium, a substance selected from the group consisting of ammonia and carbonates of ammonia in amount sufilcient to precipitate substantially all of the aluminum present in said solution, impregnating the resulting hydrous aluminum oxide precipitate with a substance selected from the group consisting of ammonium chromate and ammonium dichromate, adding to the resulting impregnated hydrous aluminum oxide from about 0.05% to 5% by weight of an alkali metal compound from the group consisting of chromates and dichromates, and then cautiously thermally decomposing the resulting product.

3. The process for forming a dehydrogenation catalyst composition which comprises adding to an aqueous aluminum salt solution, free of chromium, a substance selected from the group con' sisting of ammonia and carbonates of ammonia in amount sumc'ient to precipitate substantially all of the aluminum present in said solution, im

The precipitate was then separated impregnated hydrous aluminum oxide from about 0.05% to by wegiht of a zinc compound from the group consisting of chromates and dlchromates, and then cautiously thermally decomosing the resulting product.

4. A process for dehydrogenating hydrocarbons which comprises effecting said dehydrogenation in the presence of a catalyst composition obtained by adding to an aqueous aluminum salt solution, tree of chromium, a substance selected from the group consisting of ammonia and car- ;bonatesot ammonia in an amount sufllcient to precipitate substantially all of the aluminum present in said solution, impregnating the hydrous aluminum oxide precipitate with a. substance selected from the group consisting of ammonium chromate and ammonium dichromate, addlng to the resulting impregnated hydrous aluminum oxide a minor amount of a substance selected from the group consisting of a chromite,

REFERENCES CITED The following references are of record in the tile 0! this patent:

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